EA014251B1

EA014251B1 - A process for producing light olefins from an oxygenate-containing feedstock

Info

Publication number: EA014251B1
Application number: EA200801586A
Authority: EA
Inventors: Джон Дж. Сенетар
Original assignee: Юоп Ллк
Priority date: 2005-12-22
Filing date: 2006-12-18
Publication date: 2010-10-29
Also published as: KR101378224B1; BRPI0620346A2; CN101346328B; CN101346328A; MY150050A; KR20080077660A; WO2007111744A3; WO2007111744A2; EP1963243A2; US8163967B2; EP1963243A4; AU2006340780A1; US20070203382A1; EP1963243B1; AU2006340780B2; AR058733A1; EA200801586A1

Abstract

Improved processing of an oxygenate-containing feedstock involving increased or enhanced removal or recovery of carbonyls, particularly, acetaldehyde via either or both application of a more stringent stripping regime or addition of a sulfite-containing material.

Description

This invention relates generally to the conversion of oxygenates to olefins, and more particularly light olefins, with improved removal or extraction of carbonyl compounds and, in particular, acetaldehyde.

Most of the global petrochemical industry is interested in the production of light olefin materials and their subsequent use in the production of numerous important chemical products through polymerization, oligomerization, alkylation, and similar known chemical reactions. Light olefins include ethylene, propylene, and mixtures thereof. These light olefins are important structural units for the modern petrochemical and chemical industries. The main source of these materials in modern oil refining is steam cracking of crude oil. For various reasons, including geographic, economic, political, and supply reduction factors, technology has long sought a source other than petroleum for the huge amounts of raw materials needed to meet the demand for these light olefins materials.

The search for alternative materials for the production of light olefins has led to the use of oxygenates, such as alcohols, and more specifically to the use of methanol, ethanol and higher alcohols or their derivatives, such as, for example, dimethyl ether, diethyl ether, etc. Molecular sieves, such as microporous crystalline zeolite and non-zeolitic catalysts, especially silicon aluminophosphates (8ΆΡΘ), are known to contribute to the conversion of oxygenates into hydrocarbon mixtures, especially hydrocarbon mixtures, consisting largely of light olefins.

Such processing of oxygenates to form light olefins is commonly referred to as conversion of methanol to olefins (MTO), since methanol alone or with other oxygenate materials such as dimethyl ether (ΌΜΕ) is usually the oxygenate material most commonly used in it. Such processing typically produces or results in a set of olefin reaction products, as well as unreacted oxygenates and other residual oxygenates. Typical or common MTOs include an oxygenate absorber, whereby recycled water is used to absorb oxygenate, such as methanol and ΌΜΕ, from the product of light olefin. This oxygenate-containing circulating water is subsequently purified in an oxygenate stripper to recover methanol and ΌΜΕ, with the recovered materials eventually being returned to the oxygenate conversion reactor. The stream of dehydrated oxygenate conversion product leaving the oxygenate absorber is directed to the CO removal zone. ₂ where the stream of dehydrated oxygenate conversion product is contacted with caustic soda to remove carbon dioxide and produce a reactor product stream treated with caustic soda, namely for subsequent processing using a suitable light olefin recovery system.

Carbonyl compounds, such as acetaldehyde, are common residual oxygenates in the effluent of the oxygenate conversion reactor and are usually absorbed by circulating water. Acetaldehyde, however, is usually only incompletely distilled off in the subsequent oxygenate stripping column, so that acetaldehyde can accumulate in the circulating water. The accumulation of acetaldehyde and other carbonyl compounds in the circulating water can significantly reduce the efficiency of the oxygenate absorber for the removal of acetaldehyde and other carbonyl compounds. Incomplete removal of acetaldehyde and carbonyl compounds may result in contamination of the treated olefin products. In addition, as is known, acetaldehyde causes a malfunction in the caustic scrubber, installed further downstream from the oxygenate absorber.

Aqueous solutions of bisulfite, as is known, react with aldehydes and other carbonyl compounds, preferably methyl-substituted carbonyl compounds, to form the product of the addition of bisulfite. As long as unreacted bisulfite is present, a bisulfite addition product is formed. Sulfite, bisulfite and bisulfite addition products are usually either non-volatile, or have sufficiently low volatility to avoid their significant removal during the purification of the corresponding aqueous solutions.

Aldehydes in MTO effluent streams may, for example, contain formaldehyde, acetaldehyde, propionaldehyde, butyric aldehyde, and crotonaldehyde. These compounds may be present in the feedstock of the MTO reactor, formed as by-products, or formed during processing of the process stream from the reactor.

Aqueous sulfite solutions usually contain an equilibrium mixture of bisulfite and sulfite ions. As the pH of such solutions drops below 7.0, bisulfite becomes the dominant particle. In general, a pH below 7.0 is preferred in order to have sufficient bisulfite to react with carbonyl compounds. In general, a pH above 6.5 is preferred in order to minimize the pitting corrosion of carbon steel equipment.

In view of the foregoing, there is a need for improved processing and oxygenate to olefin conversion systems, and more specifically in such processing and system to improve the removal, extraction or separation of carbonyl compounds, such as acetaldehyde, for example, to facilitate or otherwise improve downstream processing.

- 1,014,251

Brief description of the invention

The overall objective of the invention is to provide or lead to improved processing of the original oxygenate-containing feedstock into light olefins.

A more specific objective of the invention is to overcome one or more of the problems described above.

The overall objective of the invention can be achieved, at least in part, by a method for producing light olefins from an oxygen-containing feedstock. In accordance with one preferred embodiment, such a method comprises contacting an oxygenate-containing feed in an oxygenate conversion reactor with an oxygenate conversion catalyst under reaction conditions effective for converting the oxygenate-containing feed to form an oxygenate conversion effluent containing hydrocarbons of combustible gas light olefins, C ₄₊ hydrocarbons and the remaining oxygenate materials, including the amount of carbonyl compounds. At least part of these remaining oxygenate materials, including at least part of this amount of carbonyl compounds, is absorbed by some amount of water to form a process stream of water rich in oxygenates. Subsequently, oxygenate materials are at least partially recovered from the process stream of oxygenated water to form a stream of recycled water. At least part of such extracted oxygenates can be returned back to the MTO reactor for further conversion processing if desired. At least a portion of the water from the circulating water stream forms that amount of water that is used to absorb at least a portion of the remaining oxygenate material. The method implies that the amount of treated water contains less than 150 mol.m.d. carbonyl compounds.

In accordance with another preferred embodiment, such a method comprises contacting an oxygenate-containing feed in an oxygenate conversion reactor with an oxygenate conversion catalyst under reaction conditions effective for converting the oxygenate-containing feed to form an oxygenate conversion effluent containing hydrocarbons of combustible gas light olefins, C ₄₊ hydrocarbons and remaining oxygenate materials, including some acetaldehyde. At least part of the remaining oxygenate material, including at least part of the amount of acetaldehyde, is absorbed in the amount of water to form a process stream of water enriched in the oxygenate. The oxygenate materials are subsequently at least partially recovered from the process stream of oxygenated water to form a stream of recycled water. At least a portion of the circulating water stream forms the amount of water used to absorb at least a portion of the remaining oxygenate material. The process includes the amount of water treated to a content of less than 150 mol.m.d. acetaldehyde.

The prior technology is generally unable to provide flow diagrams and placement schemes for converting oxygenate-containing feedstocks to olefins, especially light olefins, and technology that is as efficient and productive as it may be desirable to remove or remove carbonyl compounds, especially acetaldehyde, such to improve or facilitate downstream processing.

In accordance with another embodiment, a system is provided for converting oxygenates to light olefins. The system includes a reactor for contacting an oxygenate-containing feed stream with a catalyst and conversion of an oxygenate-containing feed stream to form an oxygenate conversion effluent containing fuel hydrocarbons, light olefins, C ₄₊ hydrocarbons and remaining oxygenate materials, including some acetaldehyde. An absorber is provided for absorbing at least a portion of the remaining oxygenate material in an amount of water to form an oxygenated water process stream and a stream of hydrocarbon products. The stripping column is provided for stripping the oxygenate material from the oxygenated enrichment process water stream to form a circulating water stream containing less than 150 mol. acetaldehyde and such that it can be used to absorb at least a portion of the remaining oxygenate material in the absorber. In accordance with one embodiment, the hydrocarbon product is processed to a content of less than 110 mol. acetaldehyde.

A system for converting oxygenates to light olefins in accordance with another embodiment also includes a reactor for contacting an oxygenate-containing feed stream with a catalyst and conversion of an oxygenate-containing feedstock stream to form an oxygenate conversion effluent containing fuel hydrocarbons, light olefins, C ₄₊ hydrocarbons and remaining oxygenate materials, including some acetaldehyde. The system also includes an absorber for absorbing at least a portion of the remaining oxygenate material in the amount of water to form a process stream of oxygenated water. The stripping column is provided for stripping the oxygenate material from the process stream of oxygenated water to form a stream of water. The system also includes a treatment system for treating a stream of water with a sulphite-containing material to form a stream of treated water containing not more than 150 mol ppm. acetaldehyde, along with so treated

- 1014251 water, forming the amount of water used to absorb at least part of the remaining oxygenate material in the absorber.

It should be understood that as used herein, reference to light olefins generally refers to C ₂ and C ₃ olefins, i.e. ethylene and propylene, individually or in combination.

Other objects and advantages will be apparent to those skilled in the art from the following detailed description, taken in conjunction with the appended claims and figures.

Brief description of the figures

FIG. 1 is a simplified schematic diagram of a combined oxygenate conversion process and product recovery in accordance with one preferred embodiment.

FIG. 2 is a simplified schematic of a combined oxygenate conversion process and product recovery in accordance with another preferred embodiment.

Detailed disclosure of the invention

As described above, the oxygenate-containing feedstock can be converted to olefins, and more specifically, light olefins, through a catalytic reaction. Light olefins produced or resulting from such a conversion can be removed from the oxygenate conversion reactor effluent by means of a regeneration system using water. As described in more detail below, the water used in such a treatment can optionally be returned to circulation and used further in the process after appropriate treatment to reduce the relative amount of possible undesirable characteristics such as carbonyl compounds, especially acetaldehyde.

As will be appreciated, such processing may be embodied in a variety of process flow diagrams. As a representative of FIG. 1 illustrates a simplified process flow diagram for a process flow diagram, generally designated by reference number 10, for converting oxygenates to olefins and using a water-based regeneration system using a process water treatment process in accordance with one preferred embodiment.

More specifically, the oxygenate-containing feedstock or feed stream 12, for example, typically consisting of light oxygenates, namely one or more of methanol, ethanol, dimethyl ether, diethyl ether, or a mixture thereof, is introduced into the oxygenate conversion zone or reactor section 14, in which the oxygenate-containing feedstock is contacted with the oxygenate conversion catalyst under the reaction conditions effective for the conversion of the oxygenate-containing feedstock to form the oxygenate conversion effluent containing fuel hydrocarbons for, light olefins and C ₄₊ hydrocarbons, in a manner that is known in technology, such as, for example, using a fluidized bed reactor.

As will be appreciated by those skilled in the art and the guided disclosure provided herein, such raw materials may be technical methanol, crude methanol, or any combination thereof. Crude methanol may be a crude product from a methanol synthesis plant. Those skilled in the art and guided by the disclosure provided herein will understand that, in the interests of indicators, such as improved catalyst stability, embodiments of higher purity methanol feeds may be preferred. Thus, suitable feedstocks in such embodiments may include methanol or a mixture of methanol and water, with possible feedstocks that have a methanol content between 65 and 100 wt.%, Preferably a methanol content between 80 and 100 wt.% And in accordance with one preferred embodiment, the methanol content is between 95 and 100 wt.%.

The feed stream of the methanol to olefin conversion unit may contain between 0 and 35% by weight, and more preferably between 5 and 30% by weight of water. The methanol in the feed stream may be between 70 and 100 wt.%, And more preferably between 75 and 95 wt.% Feed stream. Ethanol in the feed stream may be between 0.01 and 0.5 wt.%, And more typically between 0.1 and 0.2 wt.% Of the feed stream, although higher concentrations may be appropriate. If methanol is the main component in the feed stream, higher alcohols in the feed stream can be between 200 and 2000 ppm, and more usually between 500 and 1500 ppm. In addition, if methanol is the main component in the feed stream, dimethyl ether in the feed stream can be between 100 and 20,000 mas.d.m., and more usually between 200 and 10,000 mas.d.

However, the invention also contemplates and covers embodiments in which the oxygenate-containing feed is primarily dimethyl ether, and in certain embodiments, the oxygenate-containing feedstock is essentially dimethyl ether, either individually or with no more minor amounts of other oxygenate materials.

Reaction conditions for the conversion of oxygenates to light olefins are known to those skilled in the art. Preferably, in accordance with particular embodiments, the reaction conditions include a temperature between 200 and 700 ° C, more preferably between 300 and 600 ° C, and most preferably between 400 and 550 ° C. As those skilled in the art and those guided by the disclosure provided herein will understand, reaction conditions are usually variable, namely, dependent on the desired products. For example, if increased ethylene production is desired, it may be preferable to operate at a reactor temperature between 475 and 550 ° C, and more preferably between 500 and 520 ° C. If increased propylene production is desired, it may be preferable to operate at a reactor temperature between 350 and 475 ° C, and more preferably between 400 and 430 ° C. The resulting light olefins may have an ethylene to propylene ratio between 0.5 and 2.0, and preferably between 0.75 and 1.25. If a higher ethylene to propylene ratio is desired, then a higher reaction temperature is usually advisable than if a lower ethylene to propylene ratio would be desirable. In accordance with one preferred embodiment, the raw material temperature is preferably between 120 and 210 ° C. In accordance with another preferred embodiment, the feed temperature is preferably in the range between 180 and 210 ° C. In accordance with one preferred embodiment, it is advisable to keep the temperature below 210 ° C. so as to avoid or minimize thermal decomposition.

The oxygenate conversion reactor section 14 produces or leads to an oxygenate conversion product or effluent 16, namely in the general case containing materials of hydrocarbon products, such as hydrocarbons of combustible gas, light olefins and C ₄₊ hydrocarbons; water by-product; and the remaining oxygenates, such as methanol, dimethyl ether (ΌΜΕ) and other residual oxygenates, including carbonyl compounds, such as acetaldehyde. The oxygenate conversion effluent 16 passes into the treatment zone of the effluent 20, which results in at least a compressed vaporous oxygenate conversion 22, a liquid oxygenate conversion effluent 23, a heavily charged water 80 containing heavy oxygenates and others heavy hydrocarbons, relatively clean water flow 90 and circulating water flow 24. In practice, such a compressed oxygenate conversion effluent 22 can be the result of one or more compression stages. The circulating water stream 24 may also include water from one or more interstage condensations, as well as water from various aggregates or product recovery zones, including, for example, a wash water column, etc.

The compressed oxygenate conversion effluent 22, or at least a portion of it, is introduced into the oxygenate absorber zone 26, such as in the form of at least one absorber column. In the oxygenate absorber zone, 26 oxygenates, such as methanol, dimethyl ether (ΌΜΕ), and other residual oxygenates, including carbonyl compounds, such as acetaldehyde, are absorbed by circulating water, such as that supplied by streams 30 and 32, described in more detail below, and thus separated from the materials of the hydrocarbon product.

Thus, the zone of the absorber 26 forms or leads to a stream of oxygenated water 36, which contains such oxygenate materials in water, and a stream 40, which contains such materials a hydrocarbon product. The material stream of the hydrocarbon product 40, if desired and as described above, can be further processed as, for example, washed with caustic soda solution in the usual way to neutralize any acid gases and dried before passing the desired gas concentration into the system and regenerating the product. Gas concentration and product recovery systems that are used to process the effluent resulting from this oxygenate conversion technology are known to those skilled in the art and generally do not pose a limitation to the wider application of the invention, which will be understood by those skilled in the art and the disclosures provided herein.

The stream of oxygenated water 36 is passed to the zone of the oxygenate 44, such as in the form of at least one distillation column and one that includes a certain number of stages, namely in the form of plates or packing. In the area of the oxygenate distillate 44, at least some of the oxygenate species, such as dimethyl ether and methanol, for example, can be distilled off or otherwise efficiently removed from the water, for example, to form a stream of oxygenate-containing distillate 50, which can eventually return to the zone distillate oxygenate or reactor section 14 for further reaction processing, and the flow of circulating water 52.

Practically dimethyl ether is usually one of, if not the most volatile of oxygenate materials present in such a stream of oxygenated water. Therefore, the distillation requirement is minimal to remove only of the circulating water. Methanol is less volatile than ΌΜΕ, and depending on the degree of purification of circulating water in the zone of the oxygenate, the concentration of methanol in the circulating water will increase. Acetaldehyde is an example of a carbonyl form of residual oxygenate, such as may be present in such an oxygenate conversion effluent. Those skilled in the art and those guided by the disclosure herein will understand that acetaldehyde may be expected to cause a malfunction in a caustic scrubber, such as may optionally be located downstream of the oxygenate absorber, as described above.

In accordance with one preferred embodiment, the oxygenate 44 distillate zone is operated, for example, by including additional plates or packing, so that carbonyl compounds and especially acetaldehyde are more fully distilled off (distilled) so that the circulating water stream 52 preferably contains less than 150 mol.m. .d carbonyl compounds and acetaldehyde. In accordance with one preferred embodiment, water is optionally treated to

- 4 014251 holding less than 80 mol.m.d. carbonyl compounds and acetaldehyde. In accordance with another preferred embodiment, water is treated for a suitable content of less than 30 mol. carbonyl compounds and acetaldehyde. In addition, and what may be the result of a lower concentration of carbonyl compounds and, in particular, acetaldehyde, in the stream of circulating water 52, the flow of material of the hydrocarbon product 40 expediently contains less than 110 mol.p. carbonyl compounds and acetaldehyde. In accordance with one preferred embodiment, the hydrocarbon is expediently treated to a content of less than 50 mol ppm. carbonyl compounds and acetaldehyde. In accordance with another preferred embodiment, the hydrocarbon is treated to a suitable content of less than 20 mol ppm. carbonyl compounds and acetaldehyde.

The water of the circulating water stream 52 can subsequently be appropriately used in the appropriate process design, which may be appropriate. For example, as shown for flow chart 10 in FIG. 1, part of the circulating water stream, indicated by reference number 30, is returned to the oxygenate absorber zone 26 for contact with the compressed oxygenate conversion effluent 22, such as described above.

Another part of the circulating water stream, indicated by reference numeral 56, passes into the stripping column of wash water 60. In the stripping column of washing water 60, methanol and the remaining oxygenate are effectively removed to obtain a stream of distillate 64 containing extracted oxygenates, which can be returned to the distillate oxygenate 44 The wash water column 60 also produces a bottom water stream 68 containing a small amount of dissolved oxygenate. The portion of the bottoms stream, designated by reference number 70 and one that contains unwanted materials, can be returned to the treatment zone of the effluent 20, in which it is further processed for use in the treatment zone 20, and parts of which are removed from the process in water streams 80 and 90 , for example, in a manner known in technology. Another part of the bottom water flow, i.e. mentioned above as circulating water stream 32, may optionally be introduced into the oxygenate absorber zone 26, as described above, in order to extract additional oxygenates beyond the limitations imposed by the oxygenate content in stream 30. An additional part of the bottom water stream 68, indicated by reference number 86, may be used for washing and extraction of methanol and other oxygenates from the liquid products formed in zone 20, and ultimately return back to zone 44 through stream 24.

In another embodiment of FIG. 1, a wash water stripping column 60 can be removed. In this case, the circulating water stream 56 could be returned to the treatment zone of the effluent for use there, and its parts would be removed from the process in water streams 80 and 90. The return flow (not shown) could would be taken from the water stream 90. An absorbent stream (not shown) from such a return stream would displace the circulating water stream 32 into the oxygenate absorber 26, and the remainder of the return stream would force out stream 86 into the treatment zone of the exit stream 20. As discussed above, the distillation requirements Ke for removing ΌΜΕ from recycled water are minimal. Methanol, although less volatile than ΌΜΕ, can be effectively distilled from the wash water, because the wash water is purified in the oxygenate stripping zone. Acetaldehyde, however, is an example of a carbonyl form of residual oxygenates, such as can be present in this oxygenate conversion effluent and those that cannot be effectively removed from there without the use of a more stringent distillation than would otherwise be necessary.

To facilitate the extraction or removal of carbonyl compounds and, in particular, acetaldehyde, and as an alternative or complement to the distillation regime required in the above-described process flow diagram 10, another aspect of the invention involves processing a return or recycled water stream with a sulphite-containing material to form a treated water stream with reduced or minimized content of carbonyl compounds and, in particular, acetaldehyde.

Referring to FIG. 2, it explains a simplified flow chart for a process flow diagram, generally designated by reference number 210, for converting oxygenates to olefins and using a water-based extraction system using a process water treatment method in accordance with another preferred embodiment and uses a return or recycled water stream treatment with a sulphite-containing material to form a treated water stream with a correspondingly reduced or minimized content of carbonyl compounds and, in particular, acetaldehyde.

Scheme 210 is generally similar to process 10, described above, and having an oxygenate-containing feed or source stream 212, such as described above, that is introduced into the oxygenate conversion zone or reactor section 214, in which the oxygenate-containing feed stream is in contact with the catalyst oxygenate conversion under reaction conditions effective for converting an oxygenate-containing feed stream and forming an oxygenate effluent conversion stream containing fuel hydrocarbons light olef yns and C ₄₊ hydrocarbons, in a manner known in the art, such as, for example, using a fluidized bed reactor.

- 5 014251

As described above, the oxygenate conversion reactor section 214 produces or results in the oxygenate conversion product or the output stream 216, which generally contains hydrocarbon product materials, such as combustible hydrocarbons, light olefins and C ₄₊ hydrocarbons; water as a by-product; and the remaining oxygenates, such as methanol, dimethyl ether (ΌΜΕ) and other residual oxygenates, including carbonyl compounds, such as acetaldehyde. The oxygenate conversion effluent 216 passes into the treatment zone of the effluent 220, which leads, at least to the compressed vaporous oxygenate conversion 222 effluent, the oxygenate conversion 223 liquid effluent, a heavily charged water 280 containing heavy oxygenates and other heavy hydrocarbons, the flow of relatively pure water 290 and the flow of circulating water 224.

The compressed oxygenate conversion effluent 222, or at least a portion of it, is introduced into the oxygenate absorber zone 226, such as in the form of at least one absorber column. As in the embodiment described above, oxygenates 226 oxygenates such as methanol, dimethyl ether (ок) and other residual oxygenates, including carbonyl compounds such as acetaldehyde, can be absorbed in circulating water, as provided by streams 230 and 232 described below, in the oxygenate absorber zone. in more detail, and thus separated from the materials of the hydrocarbon product.

To facilitate the extraction or removal of carbonyl compounds and, in particular, acetaldehyde, and alternatively or in addition to the stripping mode required in the above process scheme 10, process diagram 210 processes the stream of return or recycled water with a sulfite-containing material to form a treated water stream with a correspondingly reduced or minimized content of carbonyl compounds and, in particular, acetaldehyde. Efficient treatment of a water stream with such a sulfite-containing material in accordance with one preferred embodiment can be implemented by treating the water stream with a solution of a sulfite compound containing an alkali metal or alkaline earth metal cation. Examples of such suitable cationic materials include sodium, potassium, magnesium and calcium.

References to the sulphite-containing material, which are used herein, should be understood as including sulphite compounds, bisulphite compounds and mixtures thereof. Sodium bisulfite is an example of one preferred sulfite-containing material for applying this aspect of the invention to practice.

In process design 210, such a sulfite-containing material is added to the oxygenate absorber zone 226, as indicated by the flow 234 of the sulfite-containing material from the reservoir, indicated by reference number 235. solution in the absorber pH between 1 and 10, more preferably pH between 2 and 8, and most preferably, pH between 4 to 7.

As described above, the oxygenate absorber zone 226 forms or results in a stream of oxygenated water 236, which contains such oxygenate materials in water, and a stream 240, which contains hydrocarbon product materials. The material flow of the hydrocarbon product 240, if desired and as described above, can also be treated, namely traditionally washed with a solution of caustic soda to neutralize any acid gases and dry before passing into the system a reasonable concentration of gas and regeneration of the product. The gas concentration and product recovery system used to process the effluent resulting from this oxygenate conversion technology is known to those skilled in the art and generally does not create restrictions on the wider use of the invention, as understood by those skilled in the disclosure provided herein.

The oxygenated water enriched 236 stream containing unreacted sulphite and bisulfite adducts passes to an oxygenate 244 stripping zone, such as in the form of at least one distillation column and one that includes a selected number of stages, namely in the form of plates or packing. In the area of the distillate oxygenate 244 at least part of the oxygenate species, such as dimethyl ether and methanol, for example, can be distilled or otherwise effectively removed from the water, for example, with the formation of oxygenate-containing distillate 250, which can eventually return to the oxygenate conversion zone or reactor section 214 for further reaction processing and circulating water stream 252. Unreacted sulfite and bisulfite addition products are sufficiently nonvolatile to preferably leave e in the circulating water stream 252. The stream 250 can potentially contain oxygenates, such as those derived from the decomposition of the bisulfite addition products and the products of the bisulfite entrained in the flow.

Water flow circulating water 252 can subsequently be appropriately used in the appropriate process scheme, which may be appropriate. For example, as shown for process design 210 in FIG. 2, part of the circulating water stream, indicated by reference number 230, is returned to the oxygenate absorber zone 226 for contact with the compressed exiting conversion stream

- 6 014251 oxygenate 222, such as described above.

Another part of the circulating water stream, denoted by reference number 256, passes into the stripping washing water column 260. In the washing water stripping tower 260, the methanol and the remaining oxygenates are effectively removed to form a bottoms water stream 268 containing minor amounts of dissolved oxygenate and distillate stream 264, which contains extracted oxygenates that can be returned to the oxygenate 244 distillate zone. Unreacted sulfite and bisulfite addition products are fairly nonvolatile, to preferably remain in the stream of recycled water 268.

As described above, a portion of the bottoms stream, designated by reference number 270, which contains unwanted materials, can be returned to the treatment zone of the effluent stream 220 and then processed there, while its parts are removed from the process in water streams 280 and 290, for example, in a manner known in technology. Another part of the bottoms stream, i.e., referred to as circulating water stream 232 above, may optionally be introduced into the oxygenate 226 absorber zone, as described above, in order to extract additional oxygenates beyond the limitations imposed by the oxygenate content in stream 230. Another part of the stream 268, designated by position number 286, can be used to wash and extract methanol and other oxygenates from liquid products formed in the treatment zone of the effluent stream 220, and ultimately return back to the oxygenate distillation zone 2 44 with a stream of 224. The presence of unreacted sulfite in stream 268 may be beneficial for the recovery of additional acetaldehyde and other carbonyl compounds in the treatment zone of the effluent stream 220 and the oxygenate absorber zone 226.

In accordance with such an embodiment, and alternatively or additionally to the stripping mode required in the above described process scheme 10, the extraction or removal of the desired carbonyl compound and, in particular, acetaldehyde is carried out so that the flow of return or recycled water is treated with a sulfite-containing material to form a flow treated water, expediently containing less than 150 mol.d. carbonyl compounds and acetaldehyde. In accordance with one preferred embodiment, water is optionally treated with a sulphite-containing material to form a stream of treated water containing less than 80 mol. carbonyl compounds and acetaldehyde. In accordance with another preferred embodiment, water is optionally treated with a sulphite-containing material to form a stream of treated water containing less than 30 mol. carbonyl compounds and acetaldehyde. In addition, and what may be the result of a lower concentration of carbonyl compounds and, in particular, acetaldehyde, in the stream of circulating water 252 the flow of material of the hydrocarbon product 240 expediently contains less than 110 mol.p. carbonyl compounds and acetaldehyde. In accordance with one preferred embodiment, the hydrocarbon is expediently treated to a content of less than 50 mol. ppm carbonyl compounds and acetaldehyde. In accordance with another preferred embodiment, the hydrocarbon is optionally treated to a content of less than 20 mol ppm. carbonyl compounds and acetaldehyde.

In the foregoing, it should be noted that the distillation columns of the oxygenate, i.e. 44 and 244, and the stripping columns of the wash water, i.e. 60 and 260 may be equipped with reboilers, while none of the stripping columns 44, 60, 244, 260 or absorbers 26, 226 are equipped with a chiller. However, refrigerators can be provided at least on lines 86, 286 and 56, 256.

While such an aspect of the invention has been described with specific indication of an embodiment in which sulphite-containing material is added to return or recycled water by adding oxygenate to the absorber zone, specialists and those guided by the disclosure provided herein will understand that necessarily so limited. For example, the invention may be applied using different locations or areas to add a suitable sulphite-containing material. Examples of such different locations for adding sulphite-containing material include any combination of the following locations and streams: effluent treatment zone 220, oxygenate stripper zone 244, wash water stripping column 260, and various of the above water-containing streams 224, 230, 232, 236, 252, 256 and 268.

Thus, through suitable treatment of industrial water, namely through the use of more stringent oxygenate stripping or the introduction of a suitable sulphite-containing material, or both of these methods, technological schemes and allocation schemes are provided for converting oxygenate-containing raw materials to olefins, especially light olefins, and this technology is expediently effective and productive for the removal or extraction of carbonyl compounds, especially acetaldehyde, namely improves or It is consistent processing.

The invention illustratively disclosed herein may be suitably applied in the absence of any element, part, step, component, or ingredient that is not specifically disclosed herein.

Although in the foregoing Detailed Description, this invention has been described with respect to

- 7 014251 defined preferred options for its implementation and many details were formulated for purposes of illustration, the specialist will be clear that the invention allows additional options for implementation and that some of the details described in this document can be significantly changed without departing from the basic principles of the invention.

Example.

The flow diagram of FIG. 1 of the present invention is modeled to clarify the preparation of the circulating water stream to the desired concentration of carbonyl compounds, which in this case are acetaldehyde. The compressed stream 22 is a vaporous olefin MTO product containing oxygenates, including 660 mol ppm. acetaldehyde, is introduced into the lower part of the oxygenate absorber 26 at 38 ° C. Hydrocarbon products are removed from the top 40 at 40 ° C and 19 bar (excess, gauge) for processing in a caustic scrubber further downstream to remove acidic gases. The stream enriched with oxygenates water 36 leaves the bottom of the oxygenate absorber at 40 ° C. An oxygenate water stream 36 is introduced into an oxygenate stripping column 44 with a reboiler on a plate, which is the 16th plate at the top. The oxygenate stream 50 is removed from the top to return to the oxygenate conversion reactor 14. A portion of the circulating water stream 52 at 137 ° C from the bottom of the oxygenate stripping column 44 is cooled and returned to the oxygenate absorber 26 at 40 ° C and to plate 26 from the bottom. As shown in FIG. 1, additional water is added to the upper plates in the oxygenate absorber 26 and the oxygenate stripping column 44. The molar ratio of steam to liquid in the oxygenate absorber was maintained almost constant at 0.14, and the power supplied to the oxygenate stripping reboiler was almost constant at 0, 77 kW / kg-mol of oxygenate 36 water flow, while the number of plates located below the feed plate in the oxygenate stripping column 44 was different.

If there are 25 plates located below the feed plate in the oxygenate stripping column, the concentration of acetaldehyde in the circulating water is 21 mol ppm, and in the flow of hydrocarbon products from the upper part of the oxygenate absorber is 14 mol ppm, which is advisable within the desired level is less than 20 mol.m.d.

Claims

CLAIM

1. A method of producing light olefins from an oxygenate-containing feedstock, comprising contacting the oxygenate-containing feedstock in an oxygenate conversion reactor (14, 214) with an oxygenate conversion catalyst under reaction conditions effective for converting the oxygenate-containing feedstock to form an oxygenate conversion stream containing a gas hydrocarbons , light olefins, C ₄₊ hydrocarbons and the remaining oxygenate materials, including carbonyl compounds;

absorbing at least a portion of the remaining oxygenate material, including at least a portion of the carbonyl compounds, in an amount of water to form a process stream of oxygen-rich water; and removing the oxygenate material from the oxygenated enriched process stream to form recycled water stream;

wherein at least part of the circulating water stream forms the said amount of water used to absorb at least part of the remaining oxygenate materials, and this method further includes treating the circulating water stream with a sulphite-containing material to form a treated circulating water stream containing not more than 150 mol. ppm carbonyl compounds.

2. The method according to claim 1, in which the specified amount of water is treated to a content of carbonyl compounds of less than 80 mol ppm

3. The method according to claim 1, in which the processing of the specified amount of water until the content of carbonyl compounds is not more than 150 mol ppm includes the specified extraction of oxygenate material from the process stream of water enriched with oxygenate, performed under the conditions of extraction, whereby the flow of circulating water contains not more than 150 mol. carbonyl compounds.

4. The method according to claim 1, wherein said processing of a stream of circulating water with a sulfite-containing material comprises processing the stream of circulating water with a solution of a sulfite compound containing an alkali metal or alkaline earth metal cation.

5. The method according to claim 4, in which the sulfite compound contains a sodium cation.

6. The method according to claim 4, in which the sulfite compound contains a potassium cation.

7. The method according to claim 1, in which the oxygenate-containing feedstock contains acetaldehyde.

8. The method according to claim 7, in which the absorption of at least part of the remaining oxygenate

- 8 014251 material additionally forms a stream of hydrocarbon product and the method further includes processing said hydrocarbon product to an acetaldehyde content of less than 110 mol.

9. System (210) for the conversion of oxygenates to light olefins, comprising a reactor (214) for contacting the oxygenate-containing feedstock stream with a catalyst and conversion of the oxygenate-containing feedstock stream to form an oxygenate conversion effluent containing combustible gas hydrocarbons, light olefins, С ₄₊ hydrocarbons and remaining oxygenate materials, including acetaldehyde;

an absorber (226) for absorbing at least a portion of the remaining oxygenate materials in an amount of water to form a process stream of oxygenated water;

a stripping column (244) for extracting oxygenate material from the process stream enriched with oxygenates water to form a water stream and a treatment system (226) for processing a water stream sulfite-containing material to form a stream of treated water containing not more than 150 mol. acetaldehyde;

where the treated water stream forms the amount of water used in the absorber (226) to absorb at least a portion of the remaining oxygenate material.